Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
  • C08G65/2645—Metals or compounds thereof, e.g. salts
  • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units
  • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
  • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4866—Polyethers having a low unsaturation value
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0025—Foam properties rigid

Definitions

• the present invention relates to a method for treating polypropylene ether and poly-1,2-butylene ether polyols containing double metal cyanide complex class catalyst residues to remove said residues from these polyols and additionally to provide such polyols with primary hydroxyl groups.
• Catalysts of the double-metal cyanide complex class such as zinc cobalticyanide
• Methods for making these catalysts and of using them to make polyalkylene ethers or oxides by the polymerization of alkylene oxides are disclosed in U.S. Pat. Nos. 3,278,457; 3,278,458 and 3,278,459 and divisions thereof Nos. 3,427,256; 3,427,334 and 3,427,335.
• Methods for making polyalkyleneether polyols using these double metal cyanide catalysts also, are known as shown by U.S. Pat. Nos. 3,829,505 and 3,941,849 (a division).
• polyalkyleneether polyols which exhibit higher molecular weights, higher hydroxyl functionality and lower unsaturation at the desired higher functionality and molecular weight levels than polyalkylene ether polyols produced by the use of conventional alkaline catalysts.
• These polyols also, can be made with low or high molecular weights and with low or high hydroxyl functionality so that they can be used in the manufacture of flexible to rigid polyurethane foams, rubbers, thermoplastics and thermosets.
• Polyether polyols made with alkaline catalysts have limiting molecular weights.
• a feature of the use of the double metal cyanide catalyst is the ability to get high molecular weight polypropylene ether triols in contrast to the limiting value of about 6,000 when alkali catalysts are used.
• the use of alkali catalysts to produce high molecular weight, hydroxyl terminated, polypropylene ethers results in a substantial loss in hydroxyl functionality, while when using the double metal cyanide catalyst, one is able to obtain near theoretical hydroxyl functionality (i.e. 3, if a triol is used as initiator for the PO polymerization) at even very high molecular weights.
• the double metal cyanide complex catalyst residues present in such polyols after polymerization cause certain undesirable reactions both prior to and during their use in making polyurethane products.
• polyols e.g., polypropylene ether polyols, containing the double metal cyanide complex catalyst residues
• volatiles may give an odor to the polyol and may be acetaldehyde, acetone, propionaldehyde and/or propylene oxide.
• polyurethanes from polyols containing primary hydroxyl groups.
• Primary hydroxyl groups react faster than secondary hydroxyl groups. Even when mixtures of ethylene oxide and propylene oxide are copolymerized together using the double metal cyanide complex catalyst, the end groups are principally secondary hydroxyl groups since ethylene oxide reacts faster than propylene oxide. In such copolymerizable mixtures, ethylene oxide is used in a minor molar amount, usually not over about 30 mol %, of the total alkylene oxide monomer mixture to prevent water sensitivity.
• Primary hydroxyl terminated polyols are desired since polyurethane products can be prepared from primary hydroxyl terminated polyols under less severe conditions than when they are prepared using polyols terminated with secondary hydroxyl groups.
• Another object of this invention is to provide a method for treating polyalkylene ether polyols containing double metal cyanide complex catalyst residues to remove said catalyst residues and to end cap said polyols with ethylene oxide to provide said polyols with primary hydroxyl end groups.
• removal of the double metal cyanide complex catalyst residues is accomplished by treating the catalyst residue contained in the polyols with a strong base, thereby converting it into ionic species which can be removed by ion exchange or by neutralization and filtration.
• Capping with primary hydroxyl groups is accomplished by adding ethylene oxide during or after the base treatment and prior to ion exchange or neutralization and filtration.
• the polyetherpolyols containing secondary hydroxyl groups to be treated according to the present invention comprise polyalkylene ether polyols made by the polymerization of propylene oxide or 1,2-butylene oxide or mixtures thereof, optionally said propylene oxide or 1,2-butylene oxide or mixture thereof containing a minor molar amount thereof, preferably not over about 30 mol %, of ethylene oxide.
• the polyols thus, are basically polypropylene and poly-1,2-butylene ether polyols or mixtures thereof.
• the polyetherpolyols are made according to the teaching of U.S. Pat. No. 3,829,505, above, using a catalyst of the double metal cyanide complex class, preferably zinc cobalticyanide.
• initiators or telogens there may be used ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylol propane, 1,2,6-hexane triol, hexylene glycol, tripropylene oxide adduct of glycerol or hexane triol, phloroglucinol, 4,6,4'-trihydroxy diphenyl dimethyl methane, 1,1,3-tris(4-hydroxy-phenyl) propane, pentaerythritol, pentols, hexols, for example, mannitol, glucose, fructose, sucrose, sorbitol and the like and mixtures thereof.
• Polymerization may be conducted in bulk or solvent.
• a solvent may be required when the alkylene oxide and initiator are not miscible or soluble in order to facilitate polymerization and also possibly to reduce unsaturation. Polymerization is conducted to obtain the desired molecular weight.
• the sodium or potassium metal or mixture or alloy thereof should be finely divided and should be used as a dispersion in mineral or other inert oil. If sodium or potassium per se are used, the metals should be used under inert or moisture free, or essentially moisture free, conditions to avoid reaction with water. Instead of the metals sodium hydroxide and/or potassium hydroxide can be used or aqueous solutions of sodium hydroxide and/or potassium hydroxide may be used.
• the sodium and/or potassium metal or hydroxides thereof should be used in an amount sufficient to convert at least a substantial amount of and preferably all of the double metal of the cyanide catalyst residues into ionic species which can be removed.
• the reaction of the alkali metal(s), with the presence of the ethylene oxide can be conducted in bulk or in solvent or dispersion. Reaction in solvent is preferred for ease of mixing, temperature control and so forth.
• suitable solvents or dispersants are methanol (for KOH or NaOH), tetrahydrofuran, toluene and so forth. Additionally, the use of a solvent or dispersant facilitates subsequent removal of the catalyst species or residues and the treating agent from the polyol.
• the ethylene oxide is added during or after reaction of the alkali metal with the polyol and double metal cyanide catalyst and before removal of the alkali metal and catalyst residues. Sufficient ethylene oxide is added to convert at least some and preferably all of the secondary hydroxyls of the polyols to primary hydroxyls.
• the alkali metal and ethylene oxide are reacted at a time and at a temperature sufficient to effect the conversion of the double metal cyanide catalyst residues to ionic species and to convert at least some of the secondary hydroxyl groups of the polyols to primary hydroxyl groups.
• Such reactions should be conducted in closed vessels or reactors under inert conditions such as under nitrogen, argon or helium gas and so forth.
• the reactors should be suitably equipped with heating and cooling means, stirrers, charging and discharging means and so forth.
• Removal of the ionic (metallic) species of the double metal cyanide complex catalyst residue and of the sodium and/or potassium treating agent is effected by passing the polyether polyol reaction mixture through a cationic ion exchanger or a cationic ion exchanger and then an anionic ion exchanger.
• a solvent or dispersing agent with the polyol containing the catalyst residues or ionic species and treating agent facilitates removal of the residues and agent.
• Resins are generally used as ion exchangers. Ion exchangers vary in type and size. A number of them may be used. Also, the cycle through the ion exchanger(s) may be repeated after regenerating the resin. Ion exchange materials, apparatus and methods are well known.
• the polyol containing the species and treating agent may be treated with a mineral acid like phosphoric acid or sulfuric acid to neutralize the ionic species from the catalyst residue and the treating agent and to precipitate the same. The precipitate may then be removed by filtration. Sufficient acid should be used to provide a neutral or slightly acidic polyol.
• the times and temperatures used during reaction with the Na, K etc. and with the ethylene oxide should be sufficient to obtain the desired reactions without decomposition of the polyol or the formation of deleterious by-products.
• Sufficient solvent or diluent should be used to provide for solution or dispersion of the reactants, for temperature control and for handling the reaction and final products. Solvents and the like can readily be removed at the end of the treatment by stripping or the polymer may be recovered by precipitation and so forth.
• the resulting polyol mixture is preferably stripped to remove any unreacted monomer, solvent, hydrogen cyanide and so forth.
• the polyols produced by the method of the present invention are stable or essentially stable. These polyols may be used in the manufacture of flexible to rigid polyurethane foams. Neutral polyols may react differently than acidic polyols in making foams. To make foams the polyols may be mixed with tolylene diisocyanate, water, silicone surfactant, auxiliary blowing agent if desired, stabilizers, fire retardants, catalysts(s) and so forth. Additionally, the polyetherpolyols may be used to make polyurethane elastomers, coatings and adhesives, for example, for automotive and home use such as in fascia, bumpers, paints and so forth.
• Polyethers Part I, Polyalkylene Oxides and Other Polyethers, Gaylord, Interscience Publishers, a division of John Wiley & Sons, New York, 1963; "Polyurethanes,” Chemistry and Technology, Part I, Chemistry, Saunders and Frisch, Interscience Publishers, a division of John Wiley & Sons, New York, 1962 and “Polyurethanes,” Chemistry and Technology, Part II, Technology, Saunders and Frisch, Interscience Publishers, a division of John Wiley & Sons, New York, 1964.
• triol was prepared according to the process of U.S. Pat. No. 3,829,505 by polymerizing propylene oxide using zinc hexacyanocobaltate-glyme as a catalyst and 1,2,3-tri(2-hydroxy-propoxy) propane, as the telogen to provide a polypropylene ether triol having an average molecular weight of about 3,000 and secondary hydroxyl groups. This polyol was designated as an untreated polyol.
• a portion of the untreated polyol was then reacted with a small amount of sodium metal dispersion in mineral oil and ethylene oxide, 10-15% by weight on the polyol, and then passed through a cation exchange resin and designated as a treated polyol (catalyst residues removed and containing primary OH groups).
• a treated polyol catalyst residues removed and containing primary OH groups.
• an amine stabilizer NAUGARD 445, a substituted diphenylamine antioxidant, Uniroyal Chemical
• the packing in the containers used for this analysis was a porous divinylbenzene cross-linked polystyrene, PORAPAK Q, from Waters Associates.
• the column was 9 feet long with a 3-foot section of 100-120 mesh packing and a 6-foot section of 80-100 mesh pecking.
• Table I below, the untreated polyol, even though stabilized with an amine antioxidant, developed a much higher impurity level than a commercial polyol.
• the untreated polyol was rendered free of catalyst residues, it developed close to equal amounts of impurities as the commercial sample but much less than the untreated polyol.
• Polypropylene ether triols were prepared according to the method of U.S. Pat. No. 3,829,505 from propylene oxide using VORANOL CP-260 (propylene oxide adduct of glycerol or 1,2,3-tri(-2-hydroxy-propoxy) propane, Dow Chemical Co.) as the telogen and zinc hexacyanocobaltate-glyme as the catalyst. These polyols had average molecular weights of from about 6,000 to 17,000.
• a number of these polyols were reacted with a small amount of sodium metal dispersion in mineral oil, or aqueous sodium hydroxide, and ethylene oxide (10-15% by weight on the polyol), passed through a cation exchange resin and designated as treated polyols (no catalyst residues). The others not so treated were designated as untreated polyols (with catalyst residues).
• MDI-polypropylene ether triol prepolymers containing catalyst residues exhibited higher viscosities (Poises at 25° C.) as compared to the viscosities of MDI-polypropylene ether triol free of catalyst residues prepolymers when related to the molecular weight of the polypropylene ether triol starting materials.
• Low viscosity prepolymers are generally preferred for subsequent reaction in making polyurethane elastomers and plastics.
• Heating was conducted at 74° C. for 4 hours and 50 minutes and resulted in initiation of the reaction as indicated by a pressure drop from 53 to 15 psig.
• a portion of the product was separated into a clear liquid and a solid fraction by solution in hexane and centrifugation.
• This example shows the unsatisfactory attempt to cap the polyol with ethylene oxide in any effective amount when double metal cyanide complex catalyst residues are present.
• Poly-1,2-butylene ether glycol (hydroxyl number of 47 which, assuming difunctionality (a diol) represents a molecular weight of 2380) containing zinc hexacycanocobaltate catalyst residue (200 ppm Zn) was treated with KOH and NH 4 OH and thereafter passed through an ion exchange resin. Analytical data showed that the KOH treatment (A) removed zinc more effectively than did the NH 4 OH treatment (B).
• a 10,000 g sample of polypropylene ether triol (made using "VORANOL” CP-260 as a telogen) having an OH content of 0.270 meq/g and containing zinc hexzacyanocobaltate catalyst residue (75 ppm Zn and 33 ppm Co) was treated in 2,000 g. of THF solvent with 50 g of 40% sodium dispersion in mineral oil. Thereafter, it was diluted further with a mixture of 6,650 g of isopropanol and 550 g of water and passed through 2,000 g of "AMBERLYST" A-15 (Rohm and Haas Co.) cation exchange resin. After stripping, the product was found to contain 20 ppm Zn and 12 ppm Co. This example shows removal of catalyst residues without addition of ethylene oxide. The final OH content of the polyol was 0.284 meq/g.
• Polypropylene ether triol (made using "VORANOL” CP-260 as a telogen) containing zinc hexacyanocobaltate catalyst residues (100 ppm Zn, 50 ppm Co).
• the triol was prepared using the catalyst by reaction of 12,000 g of propylene oxide and 308 g of 1,2,3-trihydroxypropoxypropane. Assuming complete reaction the triol should have had a hydroxyl content of 0.30 meq/g and a molecular weight of 10,000.
• the triol was mixed with toluene and solid KOH. The slurry was heated at 110° C. while the toluene was stripped off under vacuum. Thereafter, it was stripped 12/3 hours more, at 40 mm Hg and 110° C.
• This example shows the great reduction or removal of catalyst residues and the substantial end capping of the polypropylene ether triol. It, also, shows that non aqueous KOH can be used.
• the method of this example was the same as that of Example 6, above, except that the amounts of KOH and of toluene, per 5,000 g of polyol, were varied as shown below and as noted in Table IV below.
• Example 6 the catalyst removal process was carried out as per the previous example, Example 6. Rather than determining the zinc and cobalt concentrations, a qualitative test for the presence of potassium was employed as indicator for ion exchange efficiency. When the samples had been efficiently ion exchanged, as indicated by a negative potassium test, it may be assumed that the zinc and cobalt would have been removed as well.
• diol--used dipropylene glycol as a telogen.
• Polypropylene ether diol (using dipropylene glycol as a telogen) was prepared with zinc hexacyanocobaltate-glyme in tetrahydrofuran solution as shown below. Thereafter, sodium metal dispersion in mineral oil was added and allowed to react at 110° C. To this reaction solution, ethylene oxide was added and allowed to react at 66° C. Then, after dilution with a large amount of tetrahydrofuran and a small amount of water, the material was passed through a cation exchange resin to remove the sodium and the catalyst residues. Finally, the capped diol was vacuum stripped of tetrahydrofuran and water. The product was homogeneous and had a high primary hydroxyl content and greatly reduced zinc and cobalt contents.
• the final product was a homogeneous material.
• Capped polypropylene ether diols (using dipropylene glycol as a telogen) were prepared as in Example 8, above, at two molecular weight levels. More ethylene oxide was charged initially and longer times were allowed for it to react. In one case, this resulted in complete capping as determined by nuclear magnetic resonance analysis.

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• Chemical Kinetics & Catalysis (AREA)
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• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Toxicology (AREA)
• Polyethers (AREA)
• Polyurethanes Or Polyureas (AREA)

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Citations (9)

• 1981
  • 1981-05-22 CA CA000378141A patent/CA1155871A/en not_active Expired
  • 1981-06-22 IT IT22494/81A patent/IT1194808B/it active
  • 1981-07-21 GB GB8122463A patent/GB2085457B/en not_active Expired
  • 1981-07-22 JP JP56113814A patent/JPS5915336B2/ja not_active Expired
  • 1981-07-31 NL NLAANVRAGE8103628,A patent/NL181021C/xx not_active IP Right Cessation
  • 1981-08-14 DE DE3132258A patent/DE3132258C2/de not_active Expired
  • 1981-09-25 US US06/305,432 patent/US4355188A/en not_active Expired - Fee Related
  • 1981-10-01 FR FR8118520A patent/FR2492390A1/fr active Granted

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